JPH09208438A - Dispersing element of titanium dioxide and silicone fine particle - Google Patents
Dispersing element of titanium dioxide and silicone fine particleInfo
- Publication number
- JPH09208438A JPH09208438A JP28913296A JP28913296A JPH09208438A JP H09208438 A JPH09208438 A JP H09208438A JP 28913296 A JP28913296 A JP 28913296A JP 28913296 A JP28913296 A JP 28913296A JP H09208438 A JPH09208438 A JP H09208438A
- Authority
- JP
- Japan
- Prior art keywords
- titanium dioxide
- silicone
- fine particle
- dispersion
- dispersing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、微粒子二酸化チタ
ンをシリコーンに分散させた分散体及びこれを用いた日
焼け止め化粧料に関するものである。TECHNICAL FIELD The present invention relates to a dispersion in which fine particle titanium dioxide is dispersed in silicone, and a sunscreen cosmetic using the dispersion.
【０００２】[0002]
【従来の技術】単一粒子径約０．１５μｍ以下の微粒子
二酸化チタンは、樹脂などの膜或いは成形物に配合する
と、紫外線を遮蔽して紫外線により変質する物質を保護
する一方、可視光線を透過して透明性を有するといった
ように、単一粒子径０．１５〜０．５μｍの顔料級二酸
化チタンとは異なった性質を示すことは良く知られてい
る。更に、人体への作用が極めて低く、またそれ自体紫
外線や薬品などによる変質がほとんどないことから、微
粒子二酸化チタンは、安全性、安定性、透明性の高い紫
外線遮蔽剤として、塗料、化粧料、化学繊維に利用され
ている。ところで近年、塗料、化粧品には、耐水性、撥
水性、耐薬品性、耐候性に優れた材料として、シリコー
ンが多く利用されるようになってきた。とくに、化粧料
用には、耐水性などに加えて、肌に塗ったときの伸びの
よさ、さらっとした感触が、極めて優れていることか
ら、非常に注目されている。しかしながら、紫外線遮蔽
性を付与する目的で、シリコーン系の化粧料に二酸化チ
タンを配合しようとすると、二酸化チタン表面が親水性
であるのに対し、シリコーンが高い疎水性を有している
ことから、二酸化チタン粒子がシリコーンになじまずに
凝集してしまい、本来の透明性、紫外線遮蔽性が発揮さ
れないという問題が生じた。2. Description of the Related Art Titanium dioxide having a single particle diameter of about 0.15 μm or less, when blended with a film such as a resin or a molded product, blocks ultraviolet rays and protects substances that are altered by ultraviolet rays, while transmitting visible rays. It is well known that it exhibits different properties from pigment-grade titanium dioxide having a single particle diameter of 0.15 to 0.5 μm, such as having transparency. Furthermore, since it has a very low effect on the human body and hardly undergoes alteration by ultraviolet rays, chemicals, etc., particulate titanium dioxide is a safe, stable, highly transparent ultraviolet shielding agent for paints, cosmetics, It is used for chemical fibers. By the way, in recent years, silicone has come to be widely used as a material excellent in water resistance, water repellency, chemical resistance, and weather resistance for paints and cosmetics. In particular, for cosmetics, in addition to water resistance and the like, it has been extremely noticed because of its excellent spreadability when applied to the skin and its dry feel. However, when it is attempted to add titanium dioxide to a silicone-based cosmetic for the purpose of imparting an ultraviolet shielding property, the surface of titanium dioxide is hydrophilic, whereas silicone has high hydrophobicity. Titanium dioxide particles did not adapt to silicone and aggregated, resulting in a problem that the original transparency and ultraviolet shielding property were not exhibited.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、安全性、安
定性、透明性に優れた紫外線遮蔽剤である微粒子二酸化
チタンについて、シリコーン系の化粧料に配合したとき
に、比較的簡単な分散処理操作で高分散状態に配合し
得、非常に優れた紫外線遮蔽能を付与し得る分散体を提
供することにある。DISCLOSURE OF THE INVENTION The present invention provides a relatively simple dispersion of fine particle titanium dioxide, which is an ultraviolet shielding agent excellent in safety, stability and transparency, when blended in a silicone cosmetic. It is an object of the present invention to provide a dispersion which can be added in a highly dispersed state by a treatment operation and can impart a very excellent ultraviolet ray shielding ability.
【０００４】[0004]
【課題を解決するための手段】本発明者等は、微粒子二
酸化チタンについて、シリコーン系の化粧料に配合した
ときに、本来有する紫外線遮蔽能を完全に発揮するよう
な形態を種々検討した。その結果、分散剤を用い、シリ
コーンを媒液として、予め良く分散させた形態であれ
ば、前記問題点を解決し得るのに加え、配合した化粧料
の安定性向上、伸びのよさなど使用感の向上など、従来
技術にない優れた効果があるとの知見を得、本発明を完
成した。Means for Solving the Problems The present inventors have conducted various studies on particulate titanium dioxide in such a form that when it is blended with a silicone-based cosmetic composition, the ultraviolet ray-shielding ability originally possessed is fully exhibited. As a result, in the case of a form in which a dispersant was used and silicone was used as a liquid medium and was well dispersed in advance, the above-mentioned problems could be solved, and the stability of the blended cosmetics was improved and the feeling of use such as elongation was improved. The present invention has been completed based on the finding that it has an excellent effect that the conventional technology does not have, such as improvement of the above.
【０００５】本発明の微粒子二酸化チタン分散体は、媒
液としてのシリコーン、微粒子二酸化チタン、およびこ
の粒子を安定的に分散せしめる分散剤で構成されてい
る。The fine particle titanium dioxide dispersion of the present invention comprises silicone as a liquid medium, fine particle titanium dioxide, and a dispersant for stably dispersing these particles.
【０００６】分散体の配合としては、微粒子二酸化チタ
ン３０〜７０重量部、望ましくは４０〜７０重量部と、
分散剤が、分散剤／微粒子二酸化チタンとして１〜４０
重量％である。The composition of the dispersion is 30 to 70 parts by weight, preferably 40 to 70 parts by weight of fine particle titanium dioxide.
The dispersant is 1 to 40 as the dispersant / fine particle titanium dioxide.
% By weight.
【０００７】本発明の微粒子二酸化チタン分散体におけ
る微粒子二酸化チタンの形状は、球状、棒状、紡錘状、
樹枝状のいずれでも良く、平均単一粒子径が０．００５
〜０．１５μｍである。球状以外の形状を有する微粒子
二酸化チタンの場合には、それらの体積を求めてその体
積と等価の真球状を想定し、その径を各形状の平均単一
粒子径とした。The shape of the fine particle titanium dioxide in the fine particle titanium dioxide dispersion of the present invention is spherical, rod-shaped, spindle-shaped,
It may be dendritic, and the average single particle size is 0.005
０．１0.15 μm. In the case of fine particle titanium dioxide having a shape other than spherical, the volume thereof was determined and a spherical shape equivalent to the volume was assumed, and the diameter was defined as the average single particle diameter of each shape.
【０００８】本発明において使用する微粒子二酸化チタ
ンは、種々の方法によって製造し得るが、例えば四塩化
チタン水溶液をアルカリで中和加水分解し、得られた含
水二酸化チタンを焼成するか、あるいは含水二酸化チタ
ンを水酸化ナトリウムで加熱処理し、得られた反応生成
物を酸で加熱熟成して得ることができる。このものは、
さらに必要に応じて焼成して粒子径や粒子形状の調整、
更に耐候性の向上をはかってもよい。また、硫酸チタン
水溶液や四塩化チタン水溶液を加熱加水分解して得られ
た含水二酸化チタンを酸で解こう処理したものや、この
ものをさらに焼成したものであってもよい。さらに微粒
子二酸化チタンは、分散剤との親和性や耐光性の向上を
はかるべく、例えばアルミニウム、珪素、ジルコニウ
ム、チタン、亜鉛およびスズの少なくとも１種の酸化物
または含水酸化物で被覆されている方が好ましい。The fine particle titanium dioxide used in the present invention can be produced by various methods. For example, an aqueous solution of titanium tetrachloride is neutralized and hydrolyzed with an alkali, and the obtained hydrous titanium dioxide is calcined or hydrous dioxide is obtained. It can be obtained by heat-treating titanium with sodium hydroxide and heat-aging the obtained reaction product with an acid. This one is
Further, if necessary, it is fired to adjust the particle diameter and particle shape,
Further, the weather resistance may be improved. Also, hydrous titanium dioxide obtained by hydrolyzing an aqueous solution of titanium sulfate or an aqueous solution of titanium tetrachloride may be subjected to a peptization treatment with an acid, or a product obtained by further firing this. Further, the fine particle titanium dioxide is coated with at least one oxide or hydrous oxide of aluminum, silicon, zirconium, titanium, zinc and tin in order to improve the affinity with the dispersant and the light resistance. Is preferred.
【０００９】本発明において使用する媒液としてのシリ
コーンとしては、配合しようとする化粧料に合わせて選
択すればよく、例えば、メチルポリシロキサン、オクタ
メチルシクロテトラシロキサン、デカメチルシクロペン
タシロキサン、ドデカメチルシクロヘキサシロキサン、
メチルフェニルポリシロキサンなどが挙げられる。The silicone used as the liquid medium in the present invention may be selected according to the cosmetic to be blended, and examples thereof include methylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethyl. Cyclohexasiloxane,
Methyl phenyl polysiloxane etc. are mentioned.
【００１０】本発明において使用する分散剤は、シリコ
ーン系の化合物であることが好ましく、例えば、ジメチ
ルポリシロキサン・メチル（ポリオキシアルキレン）シ
ロキサン共重合体、トリメチルシロキシケイ酸、カルボ
キシ変性シリコーンオイル、アミノ変性シリコーンオイ
ルなどが挙げられる。シリコーン系分散剤は、酸化チタ
ンの重量基準で１〜４０％、好ましくは、５〜３０％配
合することによって、分散性、粘度、安定性等の点で良
好なシリコーン分散体が得られる。概ね、二酸チタンの
比表面積が大きいほど、また、表面被覆剤の量が多いほ
ど、分散剤の最適配合は多くなる。また、超微粒子二酸
化チタンの製法、表面被覆剤の種類によっても分散剤の
最適配合量は異なってくる。分散剤は、２種以上のもの
を組み合わせて使用した方がよい場合がある。１種だけ
の分散剤の使用では、化粧品の伸びや乳化安定性が十分
でない場合に、それらを抑えることができるからであ
る。The dispersant used in the present invention is preferably a silicone-based compound, for example, dimethylpolysiloxane / methyl (polyoxyalkylene) siloxane copolymer, trimethylsiloxysilicic acid, carboxy-modified silicone oil, amino. Examples include modified silicone oil. By blending the silicone dispersant in an amount of 1 to 40%, preferably 5 to 30% based on the weight of titanium oxide, a silicone dispersion excellent in dispersibility, viscosity, stability and the like can be obtained. In general, the greater the specific surface area of titanium diacid and the greater the amount of surface coating agent, the greater the optimal amount of dispersant compounded. In addition, the optimum blending amount of the dispersant varies depending on the manufacturing method of the ultrafine titanium dioxide and the type of the surface coating agent. In some cases, it is better to use two or more dispersants in combination. This is because the use of only one type of dispersant can suppress the elongation and the emulsion stability of cosmetics when they are not sufficient.
【００１１】次に、本発明の微粒子二酸化チタンシリコ
ーン分散体の製造方法について述べる。本発明の分散体
は、特定の分散剤、媒液及び微粒子二酸化チタンを、羽
根型攪拌機、ディスパー、ホモミキサー等を用いて予備
混合したのち、サンドミル、ペブルミル、ディスクミル
等の粉砕機を用いて、微粒子二酸化チタンを分散せしめ
ることにより得られる。なお、粉砕機の種類、粉砕メデ
ィアの選定、最適粉砕条件の設定は、高度な分散体を調
整する上で重要であるが、例えば縦型、横型のサンドミ
ルで直径０．５ｍｍのジルコニアビーズを用いて粉砕す
るのが望ましい。Next, a method for producing the fine particle titanium dioxide silicone dispersion of the present invention will be described. The dispersion of the present invention, a specific dispersant, a medium liquid and fine particles of titanium dioxide are premixed using a blade stirrer, a disper, a homomixer and the like, and then using a pulverizer such as a sand mill, a pebble mill, a disc mill. It is obtained by dispersing fine particle titanium dioxide. The type of crusher, selection of crushing media, and setting of optimum crushing conditions are important for adjusting advanced dispersions. For example, vertical and horizontal sand mills using zirconia beads with a diameter of 0.5 mm are used. It is desirable to crush it.
【００１２】このようにして得られた微粒子二酸化チタ
ンシリコーン分散体は、微粒子二酸化チタンを非常に良
く分散した状態で含有するため、化粧料に配合すると、
微粒子二酸化チタンが本来有する優れた紫外線遮蔽能を
十分に発揮するのに加え、配合した化粧料の安定性向
上、伸びのよさなどの使用感の向上の効果を発現する。The fine particle titanium dioxide silicone dispersion thus obtained contains fine particle titanium dioxide in a very well dispersed state.
In addition to sufficiently exhibiting the excellent ultraviolet ray-shielding ability inherent in fine particle titanium dioxide, it exhibits the effects of improving the stability of the blended cosmetics and improving the feeling of use such as good elongation.
【００１３】微粒子二酸化チタンシリコーン分散体は、
微粒子二酸化チタンの分散に非常に適した条件で作製さ
れたのち、所望の化粧料に配合されるため、微粒子二酸
化チタンが本来有する紫外線遮蔽能が十分に発揮され
る。これに対し、通常、化粧料に粉末を配合するような
方法で微粒子二酸化チタンを配合しても、微粒子二酸化
チタンが本来有する紫外線遮蔽能が十分発揮されないば
かりか、経時的に微粒子二酸化チタンがシリコーン成分
から分離して沈降するなどの問題が生ずることが多い。
本発明の微粒子二酸化チタンシリコーン分散体を日焼け
止め化粧料として利用する場合には、例えばシリコーン
を主とする油性成分、保湿剤、界面活性剤、顔料、香
料、防腐剤、水、アルコール類、増粘剤等と配合し、ロ
ーション状、クリーム状、ペースト状、スティック状、
乳液状など、各種の形態で用いることができる。The fine particle titanium dioxide silicone dispersion is
Since the fine particles of titanium dioxide are prepared under conditions very suitable for dispersion and then added to a desired cosmetic, the ultraviolet ray shielding ability inherent in the fine particles of titanium dioxide is sufficiently exhibited. On the other hand, normally, even if fine particle titanium dioxide is added by a method such as mixing powder into cosmetics, not only the original ultraviolet ray shielding ability of fine particle titanium dioxide is not sufficiently exerted, but also fine particle titanium dioxide is changed over time into silicone. Problems such as separation from the components and sedimentation often occur.
When the fine particle titanium dioxide silicone dispersion of the present invention is used as a sunscreen cosmetic, for example, an oily component mainly composed of silicone, a moisturizer, a surfactant, a pigment, a fragrance, a preservative, water, alcohols, an additive, etc. Mix with a sticky agent, lotion, cream, paste, stick,
It can be used in various forms such as emulsion.
【００１４】[0014]
【発明の実施の形態】本発明を下記実施例により例示し
ながら更に詳しく説明する。実施例は本発明の特定の態
様であり、限定的なものではない。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the following examples. The examples are specific embodiments of the present invention and are not limiting.
【００１５】[0015]
実施例１ 四塩化チタン水溶液（ＴｉＯ2 ２００ｇ／ｌ）を室温に
保持しながら、水酸化ナトリウム水溶液で中和してコロ
イド状の非晶質水酸化チタンを析出させ、その後熟成し
てルチル型の微小チタニアゾルを得た。このゾルを濾
過、洗浄したのち６００℃で３時間焼成し、流体エネル
ギーミルで粉砕して平均粒子径２０ｎｍの超微粒子二酸
化チタン粉末を得た。この超微粒子二酸化チタン粉末を
水中に分散させてサンドミルで湿式粉砕して超微粒子二
酸化チタンスラリー（ＴｉＯ2 ２００ｇ／ｌ）とした。
このスラリーを７０℃に加熱した後よく攪拌しながらア
ルミン酸ナトリウムをＡｌ2 Ｏ3 としてＴｉＯ2 重量基
準で５％添加し、引き続き熟成してアルミニウムの水和
酸化物を該二酸化チタン粒子上に沈殿、被覆させた。そ
の固形分を濾過、洗浄し、洗浄ケーキを乾燥したのちハ
ンマータイプミルで粉砕して超微粒子二酸化チタン粉末
（平均単一粒子径 ０．０２μｍ）を得た。Example 1 While keeping an aqueous titanium tetrachloride solution (TiO 2 200 g / l) at room temperature, it was neutralized with an aqueous sodium hydroxide solution to precipitate colloidal amorphous titanium hydroxide, and then aged to form a rutile type titanium hydroxide. A fine titania sol was obtained. The sol was filtered, washed, calcined at 600 ° C. for 3 hours, and pulverized with a fluid energy mill to obtain ultrafine titanium dioxide powder having an average particle diameter of 20 nm. The ultrafine titanium dioxide powder was dispersed in water and wet-ground with a sand mill to obtain an ultrafine titanium dioxide slurry (TiO 2 200 g / l).
After heating this slurry to 70 ° C., sodium aluminate was added as Al 2 O 3 to the titanium dioxide particles by 5% based on the weight of TiO 2 while stirring well, followed by aging to precipitate a hydrated oxide of aluminum on the titanium dioxide particles. , Coated. The solid content was filtered and washed, and the washed cake was dried and then pulverized with a hammer type mill to obtain ultrafine titanium dioxide powder (average single particle diameter 0.02 μm).
【００１６】この微粒子二酸化チタン粉末４０重量部を
分散剤（トリメチルシロキシケイ酸）１２重量部と分散
媒（オクタメチルシクロテトラシロキサン）４８重量部
との混合液中にディスパーを用いて混合した。次に、こ
れをジルコンビーズをメディアとして用い、サンドミル
で粉砕したところ、粘度１５０ｃＰのシリコーンオイル
分散体（Ａ）を得た。40 parts by weight of this fine particle titanium dioxide powder was mixed with a disperser in a mixed solution of 12 parts by weight of a dispersant (trimethylsiloxysilicic acid) and 48 parts by weight of a dispersion medium (octamethylcyclotetrasiloxane). Next, this was pulverized with a sand mill using zircon beads as a medium to obtain a silicone oil dispersion (A) having a viscosity of 150 cP.
【００１７】実施例２ 四塩化チタン水溶液の加水分解により得られた含水酸化
チタンをＴｉＯ2 換算１００ｇ／ｌの濃度の水性懸濁液
とした。この水性懸濁液２ｌに４８％水酸化ナトリウム
水溶液１４００ｇを攪拌しながら添加し、９５℃で１２
０分加熱後、ろ過し、十分に洗浄を行った。洗浄ケーキ
を水でレパルプし、ＴｉＯ2 換算１００ｇ／ｌの濃度の
水性懸濁液とし、この水性懸濁液１．５ｌを還流器付き
フラスコに入れ、３５％塩酸４００ｇを攪拌しながら添
加したのち、９５℃で１２０分間加熱熟成し、ルチル型
結晶の長軸０．２０μｍ、軸比５．０（平均単一粒子径
で表すと、０．０７８μｍ）の棒状微粒子酸化チタンの
水性懸濁液を得た。Example 2 Hydrous titanium oxide obtained by hydrolysis of an aqueous solution of titanium tetrachloride was made into an aqueous suspension having a concentration of 100 g / l in terms of TiO 2 . To 2 liters of this aqueous suspension, 1400 g of 48% aqueous sodium hydroxide solution was added with stirring, and the mixture was stirred at 95 ° C for 12 hours.
After heating for 0 minutes, it was filtered and thoroughly washed. The washed cake was repulped with water to obtain an aqueous suspension having a concentration of 100 g / l in terms of TiO 2 , 1.5 l of this aqueous suspension was placed in a flask equipped with a reflux condenser, and 400 g of 35% hydrochloric acid was added with stirring. After heating and aging at 95 ° C. for 120 minutes, an aqueous suspension of rod-shaped fine particles of titanium oxide having a long axis of rutile type crystals of 0.20 μm and an axial ratio of 5.0 (0.078 μm in terms of average single particle size) is obtained. Obtained.
【００１８】この懸濁液を７０℃に加熱した後よく攪拌
しながらアルミン酸ナトリウムをＡｌ2 Ｏ3 としてＴｉ
Ｏ2 重量基準で５％添加し、引き続き熟成してアルミニ
ウムの水和酸化物を該二酸化チタン粒子上に沈殿、被覆
させた。その固形分を濾過、洗浄し、洗浄ケーキを乾燥
したのちハンマータイプミルで粉砕して棒状微粒子二酸
化チタン粉末を得た。After heating this suspension to 70 ° C., sodium aluminate was used as Al 2 O 3 while stirring well to obtain Ti.
5% by weight of O 2 was added, followed by aging to precipitate a hydrated oxide of aluminum on the titanium dioxide particles. The solid content was filtered and washed, and the washed cake was dried and then pulverized with a hammer type mill to obtain rod-shaped fine particles of titanium dioxide powder.
【００１９】この棒状微粒子二酸化チタン粉末４０重量
部を分散剤（トリメチルシロキシケイ酸）１２重量部と
分散媒（デカメチルシクロペンタシロキサン）４８重量
部との混合液中にディスパーを用いて混合した。次に、
これをジルコンビーズをメディアとして用い、サンドミ
ルで粉砕したところ、粘度１００ｃＰのシリコーンオイ
ル分散体（Ｂ）を得た。40 parts by weight of this rod-shaped fine particle titanium dioxide powder was mixed with a disperser in a mixed solution of 12 parts by weight of a dispersant (trimethylsiloxysilicic acid) and 48 parts by weight of a dispersion medium (decamethylcyclopentasiloxane). next,
This was pulverized with a sand mill using zircon beads as a medium to obtain a silicone oil dispersion (B) having a viscosity of 100 cP.
【００２０】実施例３ 四塩化チタン水溶液の加水分解により得られた含水酸化
チタンをＴｉＯ2 換算１００ｇ／ｌの濃度の水性懸濁液
とした。この水性懸濁液２ｌに４８％水酸化ナトリウム
水溶液１４００ｇを攪拌しながら添加し、９５℃で１２
０分加熱後、ろ過し、十分に洗浄を行った。洗浄ケーキ
を水でレパルプし、ＴｉＯ2 換算１００ｇ／ｌの濃度の
水性懸濁液とし、この水性懸濁液１．５ｌを還流器付き
フラスコに入れ、３５％塩酸５７０ｇを攪拌しながら瞬
時に添加したのち、９５℃で１２０分間加熱熟成し、ル
チル型結晶の長軸０．３０μｍ、短軸０．０５５μｍ
（平均単一粒子径で表すと、０．１１μｍ）の樹枝状微
粒子酸化チタンの水性懸濁液を得た。Example 3 Hydrous titanium oxide obtained by hydrolysis of an aqueous solution of titanium tetrachloride was used as an aqueous suspension having a concentration of 100 g / l in terms of TiO 2 . To 2 liters of this aqueous suspension, 1400 g of 48% aqueous sodium hydroxide solution was added with stirring, and the mixture was stirred at 95 ° C for 12 hours.
After heating for 0 minutes, it was filtered and thoroughly washed. The washed cake is repulped with water to obtain an aqueous suspension having a concentration of 100 g / l in terms of TiO 2 , 1.5 l of this aqueous suspension is placed in a flask equipped with a reflux condenser, and 570 g of 35% hydrochloric acid is added instantaneously while stirring. After that, heat aging at 95 ° C. for 120 minutes, rutile type crystal major axis 0.30 μm, minor axis 0.055 μm
An aqueous suspension of dendritic particulate titanium oxide (expressed as an average single particle diameter of 0.11 μm) was obtained.
【００２１】この懸濁液を７０℃に加熱した後よく攪拌
しながらアルミン酸ナトリウムをＡｌ2 Ｏ3 としてＴｉ
Ｏ2 重量基準で５％添加し、引き続き熟成してアルミニ
ウムの水和酸化物を該二酸化チタン粒子上に沈殿、被覆
させた。その固形分を濾過、洗浄し、洗浄ケーキを乾燥
したのちハンマータイプミルで粉砕して樹枝状微粒子二
酸化チタン粉末を得た。After heating the suspension to 70 ° C., sodium aluminate was used as Al 2 O 3 while stirring well to obtain Ti.
5% by weight of O 2 was added, followed by aging to precipitate a hydrated oxide of aluminum on the titanium dioxide particles. The solid content was filtered, washed, and the washed cake was dried and then pulverized with a hammer type mill to obtain dendritic fine particle titanium dioxide powder.
【００２２】この樹枝状微粒子二酸化チタン粉末４０重
量部を分散剤（トリメチルシロキシケイ酸）１２重量部
と分散媒（デカメチルシクロペンタシロキサン）４８重
量部との混合液中にディスパーを用いて混合した。次
に、これをジルコンビーズをメディアとして用い、サン
ドミルで粉砕したところ、粘度１３０ｃＰのシリコーン
オイル分散体（Ｃ）を得た。40 parts by weight of this dendritic fine particle titanium dioxide powder was mixed with a disperser in a mixed solution of 12 parts by weight of a dispersant (trimethylsiloxysilicic acid) and 48 parts by weight of a dispersion medium (decamethylcyclopentasiloxane). . Next, this was pulverized with a sand mill using zircon beads as a medium to obtain a silicone oil dispersion (C) having a viscosity of 130 cP.
【００２３】実施例４ 実施例１の微粒子二酸化チタン粉末４０重量部を分散剤
（トリメチルシロキシケイ酸６重量部とジメチルポリシ
ロキサン・メチル（ポリオキシエチレン）シロキサン共
重合体６重量部）計１２重量部と分散媒（オクタメチル
シクロテトラシロキサン）４８重量部との混合液中にデ
ィスパーを用いて混合した。次に、これをジルコンビー
ズをメディアとして用い、サンドミルで粉砕したとこ
ろ、粘度９０ｃＰのシリコーンオイル分散体（Ｄ）を得
た。Example 4 A total of 12 parts by weight of 40 parts by weight of the fine titanium dioxide powder of Example 1 was added as a dispersant (6 parts by weight of trimethylsiloxysilicic acid and 6 parts by weight of dimethylpolysiloxane / methyl (polyoxyethylene) siloxane copolymer). Parts and 48 parts by weight of a dispersion medium (octamethylcyclotetrasiloxane) were mixed using a disper. Next, this was pulverized with a sand mill using zircon beads as a medium to obtain a silicone oil dispersion (D) having a viscosity of 90 cP.
【００２４】比較例１ 実施例１の微粒子二酸化チタンを粉末（Ｅ）として用い
た。Comparative Example 1 The particulate titanium dioxide of Example 1 was used as powder (E).
【００２５】比較例２ 実施例２の棒状微粒子二酸化チタンを粉末（Ｆ）として
用いた。Comparative Example 2 The rod-shaped fine particle titanium dioxide of Example 2 was used as the powder (F).
【００２６】比較例３ 実施例３の樹枝状微粒子二酸化チタンを粉末（Ｇ）とし
て用いた。Comparative Example 3 The dendritic fine particle titanium dioxide of Example 3 was used as the powder (G).
【００２７】試験例１ 微粒子二酸化チタンのシリコーン分散体（Ａ）〜（Ｄ）
及び粉末（Ｅ）〜（Ｇ）をそれぞれ下記の処方で合計量
が１００重量部になるように配合して日焼け止めクリー
ム（Ｗ／Ｏエマルジョン）（ａ）（ｂ）（ｃ）（ｄ）
（ｅ）（ｆ）（ｇ）を得た。 （１）オクタメチルシクトテトラシロキサン 残部 （２）ジメチルポリシロキサン １５．７重量部 （３）ジメチルポリシロキサン・ メチル（ポリオキシエチレン）シロキサン共重合体 ０．５重量部 （４）微粒子二酸化チタンシリコーン分散体（Ａ）〜（Ｄ） ７．５重量部 又は微粒子二酸化チタン粉末（Ｅ）〜（Ｇ） ３．０重量部 （５）ナイロンパウダー（粒子径５μｍ） １２．５重量部 （６）エタノール １０．０重量部 （７）グリセリン ２．５重量部 （８）精製水 ２７．５重量部 成分（１）〜（５）を混合してディスパーで分散したも
のに、予め混合した成分（６）〜（８）の混合物を攪拌
しながら徐々に添加して日焼け止めクリームを調整し
た。Test Example 1 Silicone dispersions of fine particle titanium dioxide (A) to (D)
And powders (E) to (G) are blended in the following formulations so that the total amount is 100 parts by weight, and sunscreen cream (W / O emulsion) (a) (b) (c) (d).
(E), (f) and (g) were obtained. (1) Octamethylsictotetrasiloxane balance (2) Dimethylpolysiloxane 15.7 parts by weight (3) Dimethylpolysiloxane / methyl (polyoxyethylene) siloxane copolymer 0.5 parts by weight (4) Fine particle titanium dioxide silicone Dispersion (A) to (D) 7.5 parts by weight or fine particle titanium dioxide powder (E) to (G) 3.0 parts by weight (5) Nylon powder (particle diameter 5 μm) 12.5 parts by weight (6) Ethanol 10.0 parts by weight (7) Glycerin 2.5 parts by weight (8) Purified water 27.5 parts by weight Components (1) to (5) are mixed and dispersed with a disper, and the components (6) are mixed in advance. The sunscreen cream was prepared by gradually adding the mixture of (8) with stirring.
【００２８】評価方法１ 上記各クリームを石英ガラス板上に２５μｍの膜厚とな
るように塗布し、分光光度計にて７５０〜３００ｎｍの
透過率を測定した。Evaluation Method 1 Each of the above creams was applied on a quartz glass plate so as to have a film thickness of 25 μm, and the transmittance of 750 to 300 nm was measured with a spectrophotometer.
【００２９】評価方法２ 上記各クリームを２０〜５２歳の女性１０名に通常に使
用してもらい、肌の上での伸びのよさの使用感を相互に
評価してもらった。以上の試験・評価結果を表１に示し
た。Evaluation method 2 Ten females aged 20 to 52 years were normally used with each of the above-mentioned creams, and they were evaluated by each other for the feeling of extension on the skin. The results of the above tests and evaluations are shown in Table 1.
【００３０】[0030]
【表１】 [Table 1]
【００３１】[0031]
【発明の効果】本発明の微粒子二酸化チタンシリコーン
分散体は、安全性、安定性、透明性に優れた紫外線遮蔽
剤である微粒子二酸化チタンを非常に良く分散した状態
で含有するため、化粧料に配合すると、微粒子二酸化チ
タンが本来有する優れた紫外線遮蔽能を十分に発揮する
のに加え、配合した化粧料の安定性向上、伸びのよさな
どの使用感の向上の効果を発現する化粧料を提供する。EFFECT OF THE INVENTION The fine particle titanium dioxide silicone dispersion of the present invention contains fine particle titanium dioxide, which is an ultraviolet shielding agent excellent in safety, stability and transparency, in an extremely well-dispersed state, so Providing cosmetics that when blended, in addition to fully exhibiting the excellent UV-blocking ability inherent in particulate titanium dioxide, the effects of improving the stability of the blended cosmetics and improving the feeling of use such as good elongation To do.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 飯田 正紀 三重県四日市市石原町１番地 石原産業株 式会社四日市事業所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masanori Iida 1 Ishihara-cho, Yokkaichi-shi, Mie Ishihara Sangyo Co., Ltd. Yokkaichi Operations
Claims (11)
化チタン粒子及び分散剤を含むシリコーン分散体で、該
微粒子二酸化チタンが平均単一粒子径０．００５〜０．
１５μｍをもつ二酸化チタン分散体。1. A silicone dispersion containing silicone as a dispersion medium, fine particle titanium dioxide particles and a dispersant, wherein the fine particle titanium dioxide has an average single particle diameter of 0.005 to 0.
Titanium dioxide dispersion with 15 μm.
０．００５〜０．１μｍである請求項１に記載の二酸化
チタン分散体。2. The titanium dioxide dispersion according to claim 1, wherein the fine titanium dioxide particles have an average single particle diameter of 0.005 to 0.1 μm.
シロキサンであるである請求項１に記載の二酸化チタン
分散体。3. The titanium dioxide dispersion according to claim 1, wherein the silicone as the dispersion medium is methyl polysiloxane.
ニルポリシロキサンであるである請求項１に記載の二酸
化チタン分散体。4. The titanium dioxide dispersion according to claim 1, wherein the silicone as the dispersion medium is methylphenyl polysiloxane.
ロポリシロキサンであるである請求項１に記載の二酸化
チタン分散体。5. The titanium dioxide dispersion according to claim 1, wherein the silicone as the dispersion medium is methylcyclopolysiloxane.
る請求項１に記載の二酸化チタン分散体。6. The titanium dioxide dispersion according to claim 1, wherein the dispersant is trimethylsiloxysilicic acid.
ル（ポリオキシアルキレン）シロキサン共重合体である
請求項１に記載の二酸化チタン分散体。7. The titanium dioxide dispersion according to claim 1, wherein the dispersant is a dimethylpolysiloxane / methyl (polyoxyalkylene) siloxane copolymer.
ジメチルポリシロキサン・メチル（ポリオキシアルキレ
ン）シロキサン共重合体である請求項１に記載の二酸化
チタン分散体。8. The titanium dioxide dispersion according to claim 1, wherein the dispersant is trimethylsiloxysilicic acid and a dimethylpolysiloxane-methyl (polyoxyalkylene) siloxane copolymer.
〜０．６μｍ、軸比が３以上の棒状微粒子二酸化チタン
である請求項１に記載の二酸化チタン分散体。9. Fine titanium dioxide particles having a length of 0.05
The titanium dioxide dispersion according to claim 1, which is a rod-shaped fine particle titanium dioxide having a particle size of ˜0.6 μm and an axial ratio of 3 or more.
いはヒトデ状であり、平均長軸径が０．２〜０．５μ
ｍ、平均短軸径が０．０４〜０．１μｍ、軸比が３以上
の棒状微粒子二酸化チタンである請求項１に記載の二酸
化チタン分散体。10. The particulate titanium dioxide is dendritic or starfish-shaped and has an average major axis diameter of 0.2 to 0.5 μm.
The titanium dioxide dispersion according to claim 1, wherein the titanium dioxide dispersion is rod-shaped fine particles of titanium dioxide having m, an average minor axis diameter of 0.04 to 0.1 µm, and an axial ratio of 3 or more.
を含有する日焼け止め化粧料。11. A sunscreen cosmetic containing the fine particle titanium dioxide dispersion according to claim 1.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28913296A JP3224750B2 (en) | 1995-11-28 | 1996-10-11 | Fine particle titanium dioxide silicone dispersion |
| PCT/JP1997/002760 WO1998016193A1 (en) | 1996-10-11 | 1997-08-07 | Dispersion of particulate titanium dioxide in silicone |
| AU37840/97A AU3784097A (en) | 1996-10-11 | 1997-08-07 | Dispersion of particulate titanium dioxide in silicone |
| TW86111438A TW409127B (en) | 1996-10-11 | 1997-08-09 | Dispersing element of titanium dioxide and poly-silicone oxide fine particle |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33392795 | 1995-11-28 | ||
| JP7-333927 | 1995-11-28 | ||
| JP28913296A JP3224750B2 (en) | 1995-11-28 | 1996-10-11 | Fine particle titanium dioxide silicone dispersion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09208438A true JPH09208438A (en) | 1997-08-12 |
| JP3224750B2 JP3224750B2 (en) | 2001-11-05 |
Family
ID=26557468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28913296A Expired - Lifetime JP3224750B2 (en) | 1995-11-28 | 1996-10-11 | Fine particle titanium dioxide silicone dispersion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3224750B2 (en) |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000053421A (en) * | 1998-08-07 | 2000-02-22 | Ishihara Sangyo Kaisha Ltd | Titanium oxide sol and its preparation |
| WO2001037795A1 (en) | 1999-11-25 | 2001-05-31 | Shiseido Co., Ltd. | Method for producing cosmetics |
| JP2002338245A (en) * | 2001-05-16 | 2002-11-27 | Tayca Corp | Dispersion with high concentration of particulate titanium oxide |
| WO2003014022A1 (en) | 2001-08-03 | 2003-02-20 | Nippon Soda Co., Ltd. | Dispersed ingredient having metal-oxygen |
| JP2007513934A (en) * | 2003-12-11 | 2007-05-31 | インペリアル・ケミカル・インダストリーズ・ピーエルシー | Metal oxide dispersion |
| WO2007069430A1 (en) | 2005-12-14 | 2007-06-21 | Shiseido Co., Ltd. | Dispersion of fine titanium oxide particles and cosmetic preparation containing the same |
| JP2007196224A (en) * | 2006-01-20 | 2007-08-09 | Samsung Electro Mech Co Ltd | Siloxane dispersion agent and nanoparticle paste composition containing the same |
| WO2007105705A1 (en) * | 2006-03-14 | 2007-09-20 | Ishihara Sangyo Kaisha, Ltd. | Visible light-responsive photocatalyst, method for producing same, photocatalyst coating agent using same, and photocatalyst dispersion |
| WO2008016029A1 (en) | 2006-07-31 | 2008-02-07 | Nippon Soda Co., Ltd. | Method for producing organic thin film by using film physical property improving process |
| WO2008059840A1 (en) | 2006-11-13 | 2008-05-22 | Nippon Soda Co., Ltd. | Method for forming organic thin film |
| KR100835865B1 (en) * | 2002-12-31 | 2008-06-09 | (주)아모레퍼시픽 | Microfine emulsion containing titanium dioxide and zinc oxide and composition of external application to the skin containing thereof |
| US7422642B2 (en) | 2002-03-12 | 2008-09-09 | Nippon Soda Co., Ltd. | Method for preparing chemical adsorption film and solution for preparing chemical adsorption film used in the method |
| EP2140945A2 (en) | 2003-04-15 | 2010-01-06 | Nippon Soda Co., Ltd. | Method for producing organic thin film |
| EP2199346A2 (en) | 2008-12-22 | 2010-06-23 | Nitto Denko Corporation | Silicone resin composition |
| JP2010150467A (en) * | 2008-12-26 | 2010-07-08 | Fujifilm Corp | Ink composition and inkjet recording method |
| JP2011032216A (en) * | 2009-08-03 | 2011-02-17 | Nippon Menaade Keshohin Kk | Solid oily cosmetic |
| US7909929B2 (en) | 2002-11-13 | 2011-03-22 | Nippon Soda Co., Ltd. | Dispersoid having metal-oxygen bonds, metal oxide film, and monomolecular film |
| EP2366521A2 (en) | 2004-12-28 | 2011-09-21 | Nippon Soda Co., Ltd. | Molding die or master pattern for electroforming each having release layer |
| WO2013057945A1 (en) | 2011-10-18 | 2013-04-25 | 日本曹達株式会社 | Surface-covered inorganic powder |
| US8568836B2 (en) | 2004-07-22 | 2013-10-29 | Nippon Soda Co., Ltd. | Organic thin film forming method, auxiliary agent for forming an organic thin film, and solution for forming an organic thin film |
| WO2014006885A1 (en) | 2012-07-05 | 2014-01-09 | 日本曹達株式会社 | Organosilicon compound, thin film forming composition using same, and organic thin film |
| JP2014091736A (en) * | 2012-11-06 | 2014-05-19 | Kao Corp | Sunscreen cosmetic |
| JP2018528225A (en) * | 2015-09-28 | 2018-09-27 | ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ | Skin care formulation comprising copolymer, inorganic metal oxide particles, and silicone |
-
1996
- 1996-10-11 JP JP28913296A patent/JP3224750B2/en not_active Expired - Lifetime
Cited By (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000053421A (en) * | 1998-08-07 | 2000-02-22 | Ishihara Sangyo Kaisha Ltd | Titanium oxide sol and its preparation |
| WO2001037795A1 (en) | 1999-11-25 | 2001-05-31 | Shiseido Co., Ltd. | Method for producing cosmetics |
| JP2002338245A (en) * | 2001-05-16 | 2002-11-27 | Tayca Corp | Dispersion with high concentration of particulate titanium oxide |
| WO2003014022A1 (en) | 2001-08-03 | 2003-02-20 | Nippon Soda Co., Ltd. | Dispersed ingredient having metal-oxygen |
| EP2218695A1 (en) | 2002-03-12 | 2010-08-18 | Nippon Soda Co., Ltd. | Method for preparing chemical adsorption film and solution for preparing chemical adsorption film for use therein |
| US7422642B2 (en) | 2002-03-12 | 2008-09-09 | Nippon Soda Co., Ltd. | Method for preparing chemical adsorption film and solution for preparing chemical adsorption film used in the method |
| US7909929B2 (en) | 2002-11-13 | 2011-03-22 | Nippon Soda Co., Ltd. | Dispersoid having metal-oxygen bonds, metal oxide film, and monomolecular film |
| KR100835865B1 (en) * | 2002-12-31 | 2008-06-09 | (주)아모레퍼시픽 | Microfine emulsion containing titanium dioxide and zinc oxide and composition of external application to the skin containing thereof |
| US8426019B2 (en) | 2003-04-15 | 2013-04-23 | Nippon Soda Co., Ltd. | Method for producing organic thin film |
| US8197906B2 (en) | 2003-04-15 | 2012-06-12 | Nippon Soda Co., Ltd. | Method for producing organic thin film |
| US7776403B2 (en) | 2003-04-15 | 2010-08-17 | Nippon Soda Co., Ltd. | Method for producing organic thin film |
| EP2140945A2 (en) | 2003-04-15 | 2010-01-06 | Nippon Soda Co., Ltd. | Method for producing organic thin film |
| EP2275211A1 (en) | 2003-04-15 | 2011-01-19 | Nippon Soda Co., Ltd. | Method for producing organic thin film |
| JP2007513934A (en) * | 2003-12-11 | 2007-05-31 | インペリアル・ケミカル・インダストリーズ・ピーエルシー | Metal oxide dispersion |
| US8568836B2 (en) | 2004-07-22 | 2013-10-29 | Nippon Soda Co., Ltd. | Organic thin film forming method, auxiliary agent for forming an organic thin film, and solution for forming an organic thin film |
| US8361375B2 (en) | 2004-12-28 | 2013-01-29 | Nippon Soda Co., Ltd. | Forming mold or electroforming mother die having release layer and method for manufacturing the same |
| EP2366521A2 (en) | 2004-12-28 | 2011-09-21 | Nippon Soda Co., Ltd. | Molding die or master pattern for electroforming each having release layer |
| WO2007069430A1 (en) | 2005-12-14 | 2007-06-21 | Shiseido Co., Ltd. | Dispersion of fine titanium oxide particles and cosmetic preparation containing the same |
| EP1974717A4 (en) * | 2005-12-14 | 2011-06-15 | Shiseido Co Ltd | Dispersion of fine titanium oxide particles and cosmetic preparation containing the same |
| US8119108B2 (en) | 2005-12-14 | 2012-02-21 | Shiseido Co., Ltd. | Dispersion of microparticulate titanium oxide and cosmetics containing the same |
| JP2007196224A (en) * | 2006-01-20 | 2007-08-09 | Samsung Electro Mech Co Ltd | Siloxane dispersion agent and nanoparticle paste composition containing the same |
| US7820584B2 (en) | 2006-03-14 | 2010-10-26 | Nihon Nohyaku Co., Ltd. | Visible light-responsive photocatalyst, method for producing same, photocatalyst coating agent using same, and photocatalyst dispersion |
| WO2007105705A1 (en) * | 2006-03-14 | 2007-09-20 | Ishihara Sangyo Kaisha, Ltd. | Visible light-responsive photocatalyst, method for producing same, photocatalyst coating agent using same, and photocatalyst dispersion |
| JP5473324B2 (en) * | 2006-03-14 | 2014-04-16 | 石原産業株式会社 | Visible light responsive photocatalyst, production method thereof, photocatalyst coating agent and photocatalyst dispersion using the same |
| WO2008016029A1 (en) | 2006-07-31 | 2008-02-07 | Nippon Soda Co., Ltd. | Method for producing organic thin film by using film physical property improving process |
| US8133546B2 (en) | 2006-07-31 | 2012-03-13 | Nippon Soda Co., Ltd. | Method for producing organic thin film by using film physical property improving process |
| WO2008059840A1 (en) | 2006-11-13 | 2008-05-22 | Nippon Soda Co., Ltd. | Method for forming organic thin film |
| US8864896B2 (en) | 2006-11-13 | 2014-10-21 | Nippon Soda Co., Ltd. | Method for forming organic thin film |
| US9416283B2 (en) | 2006-11-13 | 2016-08-16 | Nippon Soda Co., Ltd. | Method for forming organic thin film |
| US8329290B2 (en) | 2008-12-22 | 2012-12-11 | Nitto Denko Corporation | Silicone resin composition |
| EP2199346A2 (en) | 2008-12-22 | 2010-06-23 | Nitto Denko Corporation | Silicone resin composition |
| JP2010150467A (en) * | 2008-12-26 | 2010-07-08 | Fujifilm Corp | Ink composition and inkjet recording method |
| JP2011032216A (en) * | 2009-08-03 | 2011-02-17 | Nippon Menaade Keshohin Kk | Solid oily cosmetic |
| WO2013057945A1 (en) | 2011-10-18 | 2013-04-25 | 日本曹達株式会社 | Surface-covered inorganic powder |
| WO2014006885A1 (en) | 2012-07-05 | 2014-01-09 | 日本曹達株式会社 | Organosilicon compound, thin film forming composition using same, and organic thin film |
| JP2014091736A (en) * | 2012-11-06 | 2014-05-19 | Kao Corp | Sunscreen cosmetic |
| JP2018528225A (en) * | 2015-09-28 | 2018-09-27 | ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ | Skin care formulation comprising copolymer, inorganic metal oxide particles, and silicone |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3224750B2 (en) | 2001-11-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3224750B2 (en) | Fine particle titanium dioxide silicone dispersion | |
| JP4836232B2 (en) | Method for producing silica-coated fine particle titanium oxide or silica-coated fine particle zinc oxide | |
| JP2781433B2 (en) | Aqueous dispersion system of titanium dioxide and method for producing the same | |
| CA2078594C (en) | Method of preparing sunscreens | |
| KR100791555B1 (en) | A disperse system having fine powder-typed inorganic metal oxide dispersed in water and preparing method for the same | |
| JP2852487B2 (en) | Titanium dioxide aqueous dispersion | |
| JP3391802B2 (en) | Ultraviolet ray shielding fine particles, method for producing the same and cosmetics | |
| JP4105971B2 (en) | Porous titanium oxide powder and method for producing the same | |
| WO1995016637A1 (en) | Ultrafine iron-containing rutile titanium dioxide particle and process for producing the same | |
| JP2005529939A (en) | High concentration aqueous dispersion containing hydrophilic metal oxide fine particles and dispersion aid | |
| JP3894597B2 (en) | Ultrafine titanium oxide and method for producing the same | |
| JPWO2002024153A1 (en) | Metal oxide / silica composite and cosmetic containing it | |
| JP3020408B2 (en) | High concentration titanium dioxide aqueous dispersion | |
| JP2004035632A (en) | Inorganic oxide dispersion having high transparency and ultraviolet shielding ability and dispersion method | |
| JP7185143B2 (en) | Titanium dioxide aqueous dispersion and method for producing the same | |
| JPH08104606A (en) | Cosmetic | |
| JP2717904B2 (en) | Iron-containing ultrafine rutile titanium dioxide and method for producing the same | |
| JP6859949B2 (en) | Silicon oxide-coated zinc oxide, silicon oxide-coated zinc oxide-containing composition, cosmetics | |
| JP3115760B2 (en) | Iron-containing ultrafine titanium dioxide dispersion | |
| JPH09221411A (en) | Titanium dioxide and composition containing the same | |
| JP3401039B2 (en) | Cosmetics | |
| EP2356973A1 (en) | Cosmetic composition | |
| WO1998016193A1 (en) | Dispersion of particulate titanium dioxide in silicone | |
| JP3677610B2 (en) | Iron oxide-containing titanium dioxide and composition containing the same | |
| JP2008273759A (en) | Zinc oxide and method for producing the same and ultraviolet shielding composition using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080824 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090824 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100824 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100824 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110824 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120824 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120824 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130824 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130824 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140824 Year of fee payment: 13 |
|
| EXPY | Cancellation because of completion of term |